CN105037620B - A kind of preparation method of high-performance acrylic acid esters resin - Google Patents
A kind of preparation method of high-performance acrylic acid esters resin Download PDFInfo
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- CN105037620B CN105037620B CN201510102534.XA CN201510102534A CN105037620B CN 105037620 B CN105037620 B CN 105037620B CN 201510102534 A CN201510102534 A CN 201510102534A CN 105037620 B CN105037620 B CN 105037620B
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- 239000011347 resin Substances 0.000 title claims abstract description 19
- 229920005989 resin Polymers 0.000 title claims abstract description 19
- 125000005396 acrylic acid ester group Chemical group 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000000839 emulsion Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 16
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 16
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 8
- 229960000289 fluticasone propionate Drugs 0.000 claims abstract description 8
- WMWTYOKRWGGJOA-CENSZEJFSA-N fluticasone propionate Chemical compound C1([C@@H](F)C2)=CC(=O)C=C[C@]1(C)[C@]1(F)[C@@H]2[C@@H]2C[C@@H](C)[C@@](C(=O)SCF)(OC(=O)CC)[C@@]2(C)C[C@@H]1O WMWTYOKRWGGJOA-CENSZEJFSA-N 0.000 claims abstract description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 229930182478 glucoside Natural products 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- NSRKPHLHEMCETL-UHFFFAOYSA-N 5-(2-phenylethenyl)benzene-1,2,3,4-tetrol Chemical compound OC1=C(O)C(O)=CC(C=CC=2C=CC=CC=2)=C1O NSRKPHLHEMCETL-UHFFFAOYSA-N 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 7
- 239000003599 detergent Substances 0.000 claims description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- IRECWLYBCAZIJM-UHFFFAOYSA-N Flumiclorac pentyl Chemical group C1=C(Cl)C(OCC(=O)OCCCCC)=CC(N2C(C3=C(CCCC3)C2=O)=O)=C1F IRECWLYBCAZIJM-UHFFFAOYSA-N 0.000 claims description 4
- 229940095758 cantharidin Drugs 0.000 claims description 4
- DHZBEENLJMYSHQ-XCVPVQRUSA-N cantharidin Chemical compound C([C@@H]1O2)C[C@@H]2[C@]2(C)[C@@]1(C)C(=O)OC2=O DHZBEENLJMYSHQ-XCVPVQRUSA-N 0.000 claims description 4
- 229930008397 cantharidin Natural products 0.000 claims description 4
- DHZBEENLJMYSHQ-UHFFFAOYSA-N cantharidine Natural products O1C2CCC1C1(C)C2(C)C(=O)OC1=O DHZBEENLJMYSHQ-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- BWXTYVZNIVMDCG-UHFFFAOYSA-N C1=CC=CC1.C1=CC=CC1.[O-2].[O-2].[Ti+4] Chemical compound C1=CC=CC1.C1=CC=CC1.[O-2].[O-2].[Ti+4] BWXTYVZNIVMDCG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 102000006995 beta-Glucosidase Human genes 0.000 claims description 3
- 108010047754 beta-Glucosidase Proteins 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims 1
- 210000003608 fece Anatomy 0.000 claims 1
- 239000004925 Acrylic resin Substances 0.000 abstract description 20
- 229920000178 Acrylic resin Polymers 0.000 abstract description 20
- 230000007547 defect Effects 0.000 abstract description 4
- 206010023126 Jaundice Diseases 0.000 abstract description 2
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical class NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 abstract 1
- -1 stilbene glucoside Chemical class 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- BKOOMYPCSUNDGP-UHFFFAOYSA-N trimethyl-ethylene Natural products CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000012425 OXONE® Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- IYRMWMYZSQPJKC-UHFFFAOYSA-N kaempferol Chemical compound C1=CC(O)=CC=C1C1=C(O)C(=O)C2=C(O)C=C(O)C=C2O1 IYRMWMYZSQPJKC-UHFFFAOYSA-N 0.000 description 4
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 4
- UXTPZTMLGJSGEH-UHFFFAOYSA-N 1,1,1-trifluoro-N-methylbut-3-en-2-amine Chemical compound CNC(C=C)C(F)(F)F UXTPZTMLGJSGEH-UHFFFAOYSA-N 0.000 description 3
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- LHWSEFCIRYVTLZ-UHFFFAOYSA-N 4,4,4-trifluorobut-2-enenitrile Chemical compound FC(F)(F)C=CC#N LHWSEFCIRYVTLZ-UHFFFAOYSA-N 0.000 description 2
- RKWHWFONKJEUEF-GQUPQBGVSA-O Cyanidin 3-O-glucoside Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC2=C(O)C=C(O)C=C2[O+]=C1C1=CC=C(O)C(O)=C1 RKWHWFONKJEUEF-GQUPQBGVSA-O 0.000 description 2
- UBSCDKPKWHYZNX-UHFFFAOYSA-N Demethoxycapillarisin Natural products C1=CC(O)=CC=C1OC1=CC(=O)C2=C(O)C=C(O)C=C2O1 UBSCDKPKWHYZNX-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KZFUWRMVPLBQKD-UHFFFAOYSA-N but-2-en-2-amine Chemical compound CC=C(C)N KZFUWRMVPLBQKD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- YTMNONATNXDQJF-UBNZBFALSA-N chrysanthemin Chemical compound [Cl-].O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC2=C(O)C=C(O)C=C2[O+]=C1C1=CC=C(O)C(O)=C1 YTMNONATNXDQJF-UBNZBFALSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 description 2
- 235000008777 kaempferol Nutrition 0.000 description 2
- UXOUKMQIEVGVLY-UHFFFAOYSA-N morin Natural products OC1=CC(O)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UXOUKMQIEVGVLY-UHFFFAOYSA-N 0.000 description 2
- UZHSEJADLWPNLE-GRGSLBFTSA-N naloxone Chemical compound O=C([C@@H]1O2)CC[C@@]3(O)[C@H]4CC5=CC=C(O)C2=C5[C@@]13CCN4CC=C UZHSEJADLWPNLE-GRGSLBFTSA-N 0.000 description 2
- 229960004127 naloxone Drugs 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000021286 stilbenes Nutrition 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- TVZGACDUOSZQKY-LBPRGKRZSA-N 4-aminofolic acid Chemical compound C1=NC2=NC(N)=NC(N)=C2N=C1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 TVZGACDUOSZQKY-LBPRGKRZSA-N 0.000 description 1
- LMNPKIOZMGYQIU-UHFFFAOYSA-N 5-(trifluoromethyl)-1h-pyrimidine-2,4-dione Chemical compound FC(F)(F)C1=CNC(=O)NC1=O LMNPKIOZMGYQIU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229960003896 aminopterin Drugs 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to the preparation method of a kind of high-performance acrylic acid esters resin, add water, dodecylbenzene sodium sulfonate, fatty alcohol-polyoxyethylene ether, 2 acrylamide 2 methyl propane sulfonic acids, heat up stirring, adds A monomer, emulsifying 40min, it is warmed up to 70 DEG C and starts logical recirculation water, it is warmed up to 85 DEG C and adds potassium persulfate solution, react 2h, add FLUTICASONE PROPIONATE, stirring reaction, obtains stratum nucleare emulsion；It is simultaneously added dropwise B monomer and potassium persulfate solution in gained stratum nucleare emulsion, drip stirring reaction, cool to 50 DEG C, add dodecylbenzene sodium sulfonate and fatty alcohol-polyoxyethylene ether, response time 70min, 70 DEG C of reaction 1h, adding ammonia adjusts pH value to 7 ~ 8, obtaining acrylic resin, this preparation method both can make acrylic resin wearability be greatly improved, and can improve again the defect of acrylic resin emulsion film forming jaundice.
Description
Technical field
The present invention relates to the preparation method of a kind of acrylic resin, particularly to a kind of high-performance acrylic acid esters tree
The preparation method of fat.
Background technology
Acrylic resin group coating to be used as, adhesive and finishing agent, the market of its maximum is car paint, and this is external
Light industry, household electrical appliance, metal household implements, aluminum products, coiled material industry, instrument and meter, build, textile, plastic, wooden
The industry such as product, papermaking is all widely used.The direction of acrylic resin coating hydrotropismization, multifunction and high function is sent out
Exhibition.
But acrylic resin abrasion resisting poor performance, emulsion film forming somewhat turn to be yellow, it is therefore desirable to be modified it, protect
Protect the safety of lives and properties.
Water-soluble medium makes acrylate containing fluorine resin wetted and has mobility, and high boiling solvent then rises and is dried delay
The effect of agent, after application during drying and sintering, can prevent film from chapping.Even if high boiling solvent is under fluororesin forming temperature
Evaporation, does not the most produce impact to film.
Summary of the invention
It is desirable to provide the preparation method of a kind of high-performance acrylic acid esters resin, select 2-acrylamide-2-first
Base propane sulfonic acid substitutes traditional acrylic or methacrylic acid, improves associativity and the dispersibility of stratum nucleare, with fluorine class wear resistence list
Body is aggregated on the main chain of acrylic resin, and epoxide and amino graft polymerization are to acrylic resin main chain
On, by FLUTICASONE PROPIONATE, remaining persulfate is processed, improve acrylic resin emulsion film forming and somewhat send out
Yellow defect, selects slaine to have acrylic resin to cross-link simultaneously, improves the wearability of acrylic resin.
The present invention is by the following technical solutions:
1. the preparation method of a high-performance acrylic acid esters resin, it is characterised in that:
(1) in the 250ml there-necked flask with agitator, thermometer and condensing tube, water 65g, detergent alkylate sulphur are added
Acid sodium 0.55g, fatty alcohol-polyoxyethylene ether 0.25g, 2-acrylamide-2-methyl propane sulfonic 0.3g, be warming up to 50 DEG C, stirring
40min, adds A monomer, emulsifying 40min, is warmed up to 70 DEG C and starts logical recirculation water, is warmed up to 85 DEG C of water-soluble mistakes of dropping 8g
Potassium sulfate solution 8.2g, time for adding 1h, drip reaction 2h, add cantharidin 1g and FLUTICASONE PROPIONATE 0.3g, and 75
DEG C stirring reaction 2h, obtain stratum nucleare emulsion；
Described A monomer is by perfluorinated allyl base benzene 3g, butyl acrylate 2g, 2-(Acryloyloxy)ethanol 3g, ethyl acrylate
3.0g and acrylamide 4g mixes；
(2) in step (1) gained stratum nucleare emulsion, B monomer it is simultaneously added dropwise and with the water-soluble potassium persulfate solution of 8g
8.2g, time for adding 1h, drip 80 DEG C of stirring reaction 2h, adds titanium dioxide dicyclopentadiene 0.5g, 75 DEG C of reaction 2h,
Cool to 50 DEG C, add dodecylbenzene sodium sulfonate 0.395g and fatty alcohol-polyoxyethylene ether 0.135g, response time 70min,
Add beta-glucosidase 0.02g and Alumen 0.21g, 70 DEG C of reaction 1h, add ammonia and adjust pH value to 7 ~ 8, obtain described high-performance
Acrylic resin；
Described B monomer is by Flumiclorac pentyl 4g, butyl acrylate 3g, 2-(Acryloyloxy)ethanol 4.0g, 2-(Acryloyloxy)ethanol
4.0g, styrene 0.6g, allyl dichloride amine 1g and 2,3,5,4-tetrahydroxystilbene glucoside 3g mixing composition.
The preparation method of 2 one kinds of high-performance acrylic acid esters resins, it is characterised in that:
(1) in the 250ml there-necked flask with agitator, thermometer and condensing tube, water 85g, detergent alkylate sulphur are added
Acid sodium 2.5g, fatty alcohol-polyoxyethylene ether 0.6g, 2-acrylamide-2-methyl propane sulfonic 3.2g, be warming up to 40 DEG C, stirring
40min, adds A monomer, emulsifying 60min, is warmed up to 70 DEG C and starts logical recirculation water, is warmed up to 80 DEG C, and dropping 8g is water-soluble
Ammonium persulfate solution 8.6g, time for adding 2h, drip reaction 2h, add 1,2-epoxy-4-vinyl cyclohexane 4g and fluorine
For Kazon propionic ester 0.3g, 80 DEG C of stirring reaction 2h, obtain stratum nucleare emulsion；
Described A monomer is by 3-methylamino-4,4,4-trifluorobutene acetoacetic ester 6g, 3-perfluoro capryl 2-acrylic acid hydroxypropyl
Ester 7g, methyl methacrylate 7g, ethyl acrylate 5g and 2,3,5,4-tetrahydroxystilbene glucoside 7g mix；
(2) in step (1) gained stratum nucleare emulsion, B monomer it is simultaneously added dropwise and with the water-soluble ammonium persulfate solution of 8g
8.8g, time for adding 2h, drip insulation 80 DEG C stirring reaction 2h, add cyanidin-3-O-glucoside 2.2g, 85 DEG C
Response time 3h, cools to 50 DEG C, adds dodecylbenzene sodium sulfonate 0.375g and fatty alcohol-polyoxyethylene ether 0.125g, reaction
Time 60min, adds epoxychloropropane 0.4g and Disulfatozirconic acid. 0.36g, 70 DEG C of reaction 1h, adds ammonia and adjusts pH value to 7 ~ 8, obtains described
High-performance acrylic acid esters resin；
Described B monomer is by 4,4,4-trifluorobutene nitrile 7g, 3-perfluoro capryl 2-Hydroxypropyl acrylate 6g, methacrylic acid
Methyl ester 6.5g, 2-(Acryloyloxy)ethanol 7.5g, styrene 1.5g, N, N-di-2-ethylhexylphosphine oxide methyl-prop enamine 3.2g and 2,3,5,4-tetra-hydroxyl
Base stilbene glucoside 5g mixes composition.
The preparation method of 3 one kinds of high-performance acrylic acid esters resins, it is characterised in that:
(1) in the 250ml there-necked flask with agitator, thermometer and condensing tube, water 75g, detergent alkylate sulphur are added
Acid sodium 0.99, fatty alcohol-polyoxyethylene ether 0.36g and 2-acrylamide-2-methyl propane sulfonic 1.8g, be warming up to 40 DEG C, stirring
30min, adds A monomer, emulsifying 45min, is warmed up to 70 DEG C and starts logical recirculation water, is warmed up to 80 DEG C, and dropping 6g is water-soluble
Potassium monopersulfate solutions 6.8g, time for adding 2.5h, drip reaction 2.5h, add 1, and 1,1-tri-fluoro-2,3-epoxy third
Alkane 3g and FLUTICASONE PROPIONATE 0.6g, stirring reaction 3h, obtain stratum nucleare emulsion；
Described A monomer is by 4-bromo-3,3,4,4-tetrafluoro butylene 3.5g, butyl acrylate 5.5g, methacrylic acid hydroxypropyl
Base ester 4g, ethyl acrylate 3g, 3-methyl-2-butene amine 3.2g, 2,3,5,4-tetrahydroxystilbene glucoside 4.5g are mixed
Conjunction forms；
(2) in step (1) gained stratum nucleare emulsion, B monomer it is simultaneously added dropwise and with the water-soluble potassium monopersulfate solutions of 8g
8.45g, time for adding 1.5h, drip 80 DEG C of stirring reaction 2h, add kaempferol 0.8g, 80 DEG C of response time 1 ~ 3h, fall
Temperature, to 50 DEG C, adds dodecylbenzene sodium sulfonate 0.375g and fatty alcohol-polyoxyethylene ether 0.125g, response time 60min, adds
Enter naloxone 0.25g and potassium ferricyanide 0.32g, 70 DEG C of reaction 1h, add ammonia and adjust pH value to 7 ~ 8, obtain described high-performance acrylic acid
Esters resin；
Described B monomer is by the bromo-4-of 5-chloro-4,5,5-trifluoro amylene 2.6g, butyl acrylate 4.5g, hydroxyethyl methacrylate
Propyl diester 4.9g, 2-(Acryloyloxy)ethanol 4.9g and 2,3,5,4-tetrahydroxystilbene glucoside 3g mixing composition.
The beneficial effects of the present invention is:
(1) the wearability acrylic resin prepared by, has stronger wearability, and the film forming of gained emulsion is transparent,
Improve tradition persulfate and do the defect of acrylic resin emulsion film forming jaundice prepared by initiator；
(2) perfluorinated allyl base benzene, 3-methylamino-4,4,4-trifluorobutene acetoacetic ester, 4-bromo-3,3,4,4-tetrafluoro are selected
The fluorochemical monomers such as the bromo-4-of butylene, 5-chloro-4,5,5-trifluoro amylene and slaine (Alumen, Disulfatozirconic acid., potassium ferricyanide) improve acrylic acid
The wearability of esters resin；
(3) under stratum nucleare and shell act on jointly, improve the wearability of acrylic resin；
(4) remaining persulfate is processed by FLUTICASONE PROPIONATE, improves acrylic resin emulsion film forming
The defect somewhat turned to be yellow；
(5) epoxide such as cantharidin, 1,2-epoxy-4-vinyl cyclohexane, 1,1,1-tri-fluoro-2,3-expoxy propane
React with the amino of acrylic resin, make the side chain of resin also have good wearability；
(6) Flumiclorac pentyl also makes acrylic resin have certain light resistance.
Detailed description of the invention
In order to be more fully understood that and implement the present invention, further illustrate the present invention below in conjunction with specific embodiment.
Example 1
(1) in the 250ml there-necked flask with agitator, thermometer and condensing tube, water 65g, detergent alkylate sulphur are added
Acid sodium 0.55g, fatty alcohol-polyoxyethylene ether 0.25g, 2-acrylamide-2-methyl propane sulfonic 0.3g, be warming up to 50 DEG C, stirring
40min, adds A monomer, emulsifying 40min, is warmed up to 70 DEG C and starts logical recirculation water, is warmed up to 85 DEG C of water-soluble mistakes of dropping 8g
Potassium sulfate solution 8.2g, time for adding 1h, drip reaction 2h, add cantharidin 1g and FLUTICASONE PROPIONATE 0.3g, and 75
DEG C stirring reaction 2h, obtain stratum nucleare emulsion；
Described A monomer is by perfluorinated allyl base benzene 3g, butyl acrylate 2g, 2-(Acryloyloxy)ethanol 3g, ethyl acrylate
3.0g and acrylamide 4g mixes；
(2) in step (1) gained stratum nucleare emulsion, B monomer it is simultaneously added dropwise and with the water-soluble potassium persulfate solution of 8g
8.2g, time for adding 1h, drip 80 DEG C of stirring reaction 2h, adds titanium dioxide dicyclopentadiene 0.5g, 75 DEG C of reaction 2h,
Cool to 50 DEG C, add dodecylbenzene sodium sulfonate 0.395g and fatty alcohol-polyoxyethylene ether 0.135g, response time 70min,
Add beta-glucosidase 0.02g and Alumen 0.21g, 70 DEG C of reaction 1h, add ammonia and adjust pH value to 7 ~ 8, obtain described high-performance
Acrylic resin；
Described B monomer is by Flumiclorac pentyl 4g, butyl acrylate 3g, 2-(Acryloyloxy)ethanol 4.0g, 2-(Acryloyloxy)ethanol
4.0g, styrene 0.6g, allyl dichloride amine 1g and 2,3,5,4-tetrahydroxystilbene glucoside 3g mixing composition.
Example 2
(1) in the 250ml there-necked flask with agitator, thermometer and condensing tube, water 85g, detergent alkylate sulphur are added
Acid sodium 2.5g, fatty alcohol-polyoxyethylene ether 0.6g, 2-acrylamide-2-methyl propane sulfonic 3.2g, be warming up to 40 DEG C, stirring
40min, adds A monomer, emulsifying 60min, is warmed up to 70 DEG C and starts logical recirculation water, is warmed up to 80 DEG C, and dropping 8g is water-soluble
Ammonium persulfate solution 8.6g, time for adding 2h, drip reaction 2h, add 1,2-epoxy-4-vinyl cyclohexane 4g and fluorine
For Kazon propionic ester 0.3g, 80 DEG C of stirring reaction 2h, obtain stratum nucleare emulsion；
Described A monomer is by 3-methylamino-4,4,4-trifluorobutene acetoacetic ester 6g, 3-perfluoro capryl 2-acrylic acid hydroxypropyl
Ester 7g, methyl methacrylate 7g, ethyl acrylate 5g and 2,3,5,4-tetrahydroxystilbene glucoside 7g mix；
(2) in step (1) gained stratum nucleare emulsion, B monomer it is simultaneously added dropwise and with the water-soluble ammonium persulfate solution of 8g
8.8g, time for adding 2h, drip insulation 80 DEG C stirring reaction 2h, add cyanidin-3-O-glucoside 2.2g, 85 DEG C
Response time 3h, cools to 50 DEG C, adds dodecylbenzene sodium sulfonate 0.375g and fatty alcohol-polyoxyethylene ether 0.125g, reaction
Time 60min, adds epoxychloropropane 0.4g and Disulfatozirconic acid. 0.36g, 70 DEG C of reaction 1h, adds ammonia and adjusts pH value to 7 ~ 8, obtains described
High-performance acrylic acid esters resin；
Described B monomer is by 4,4,4-trifluorobutene nitrile 7g, 3-perfluoro capryl 2-Hydroxypropyl acrylate 6g, methacrylic acid
Methyl ester 6.5g, 2-(Acryloyloxy)ethanol 7.5g, styrene 1.5g, N, N-di-2-ethylhexylphosphine oxide methyl-prop enamine 3.2g and 2,3,5,4-tetra-hydroxyl
Base stilbene glucoside 5g mixes composition.
Example 3
(1) in the 250ml there-necked flask with agitator, thermometer and condensing tube, water 75g, detergent alkylate sulphur are added
Acid sodium 0.99, fatty alcohol-polyoxyethylene ether 0.36g and 2-acrylamide-2-methyl propane sulfonic 1.8g, be warming up to 40 DEG C, stirring
30min, adds A monomer, emulsifying 45min, is warmed up to 70 DEG C and starts logical recirculation water, is warmed up to 80 DEG C, and dropping 6g is water-soluble
Potassium monopersulfate solutions 6.8g, time for adding 2.5h, drip reaction 2.5h, add 1, and 1,1-tri-fluoro-2,3-epoxy third
Alkane 3g and FLUTICASONE PROPIONATE 0.6g, stirring reaction 3h, obtain stratum nucleare emulsion；
Described A monomer is by 4-bromo-3,3,4,4-tetrafluoro butylene 3.5g, butyl acrylate 5.5g, methacrylic acid hydroxypropyl
Base ester 4g, ethyl acrylate 3g, 3-methyl-2-butene amine 3.2g, 2,3,5,4-tetrahydroxystilbene glucoside 4.5g are mixed
Conjunction forms；
(2) in step (1) gained stratum nucleare emulsion, B monomer it is simultaneously added dropwise and with the water-soluble potassium monopersulfate solutions of 8g
8.45g, time for adding 1.5h, drip 80 DEG C of stirring reaction 2h, add kaempferol 0.8g and aminopterin 0.21g, 80 DEG C
Response time 1 ~ 3h, cools to 50 DEG C, adds dodecylbenzene sodium sulfonate 0.375g and fatty alcohol-polyoxyethylene ether 0.125g, instead
60min between Ying Shi, adds naloxone 0.25g, potassium ferricyanide 0.32g and 5-trifluoromethyl uracil 0.17g, 70 DEG C of reaction 1h, adds
Ammonia adjusts pH value to 7 ~ 8, obtains described high-performance acrylic acid esters resin；
Described B monomer is by the bromo-4-of 5-chloro-4,5,5-trifluoro amylene 2.6g, butyl acrylate 4.5g, hydroxyethyl methacrylate
Propyl diester 4.9g, 2-(Acryloyloxy)ethanol 4.9g and 2,3,5,4-tetrahydroxystilbene glucoside 3g mixing composition.
Beneficial effects of the present invention is further illustrated below by relevant experimental data:
Table 1 high-performance acrylic acid esters resin institute's film forming elongation at break and outward appearance
| Experimental group | Market ARB | Example 1 | Example 2 | Example 3 |
| Elongation at break/% | 90.07 | 149.78 | 132.63 | 126.69 |
| Film outward appearance | Light yellow | Water white transparency | Water white transparency | Water white transparency |
Table 1 middle finger object detection method reference: Jiang Weiqi. leather finish physical and chemical inspection [M]. China Light Industry Press,
1999,82-96.Employ wearability resin molding of the present invention, elongation at break be improved significantly.
The abrasion performance of table 2 high-performance acrylic acid esters resin institute film forming
| Experimental group | Market ARB | Example 1 | Example 2 | Example 3 |
| Abrasion loss/mg | 34 | 28 | 23 | 21 |
Note: use 120# sand round
The data of table 2 are to carry out under GB1768-89 paint film abrasion performance assay method, and wear-resisting those at least is best, real
The abrasivity of example is preferable.
Claims (1)
1. the preparation method of a high-performance acrylic acid esters resin, it is characterised in that:
(1) in the 250ml there-necked flask with agitator, thermometer and condensing tube, water 65g, detergent alkylate sulphur are added
Acid sodium 0.55g, fatty alcohol-polyoxyethylene ether 0.25g, 2-acrylamide-2-methyl propane sulfonic acid 0.3g, be warming up to 50
DEG C, stir 40min, add A monomer, emulsifying 40min, be warmed up to 70 DEG C and start logical recirculation water, be warmed up to 85 DEG C of droppings
With 8g water-soluble potassium persulfate solution 8.2g, time for adding 1h, drip reaction 2h, add cantharidin 1g and
FLUTICASONE PROPIONATE 0.3g, 75 DEG C of stirring reaction 2h, obtain stratum nucleare emulsion；
Described A monomer is by perfluorinated allyl base benzene 3g, butyl acrylate 2g, 2-(Acryloyloxy)ethanol 3g, ethyl acrylate
3.0g and acrylamide 4g mixes；
(2) in step (1) gained stratum nucleare emulsion, B monomer it is simultaneously added dropwise and with the water-soluble potassium persulfate solution of 8g
8.2g, time for adding 1h, drip 80 DEG C of stirring reaction 2h, add titanium dioxide dicyclopentadiene 0.5g, and 75 DEG C anti-
Answer 2h, cool to 50 DEG C, add dodecylbenzene sodium sulfonate 0.395g and fatty alcohol-polyoxyethylene ether 0.135g, reaction
Time 70min, adds β-glucosidase 0.02g and Alumen 0.21g, 70 DEG C of reaction 1h, adds ammonia and adjust pH value extremely
7 ~ 8, obtain described high-performance acrylic acid esters resin；
Described B monomer is by Flumiclorac pentyl 4g, butyl acrylate 3g, 2-(Acryloyloxy)ethanol 4.0g, 2-(Acryloyloxy)ethanol
4.0g, styrene 0.6g, allyl dichloride amine 1g and 2,3,5,4-tetrahydroxystilbene glucoside 3g mixing group
Become.
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